EP2491458A2 - Procédés de fabrication de structures à motifs à partir de matériaux polymères contenant du fluor et polymères contenant du fluor - Google Patents

Procédés de fabrication de structures à motifs à partir de matériaux polymères contenant du fluor et polymères contenant du fluor

Info

Publication number
EP2491458A2
EP2491458A2 EP10825580A EP10825580A EP2491458A2 EP 2491458 A2 EP2491458 A2 EP 2491458A2 EP 10825580 A EP10825580 A EP 10825580A EP 10825580 A EP10825580 A EP 10825580A EP 2491458 A2 EP2491458 A2 EP 2491458A2
Authority
EP
European Patent Office
Prior art keywords
fluorine
layer
moiety
pattern
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP10825580A
Other languages
German (de)
English (en)
Other versions
EP2491458A4 (fr
Inventor
Christopher Ober
George Malliaras
Jin-Kyun Lee
Hon Hang Fong
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cornell University
Original Assignee
Cornell University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cornell University filed Critical Cornell University
Publication of EP2491458A2 publication Critical patent/EP2491458A2/fr
Publication of EP2491458A4 publication Critical patent/EP2491458A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
    • H10K71/221—Changing the shape of the active layer in the devices, e.g. patterning by lift-off techniques
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/115—Polyfluorene; Derivatives thereof
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/151—Copolymers

Definitions

  • the present invention generally relates to patterning of fluorine-containing materials and patterned structures of fluorine-containing materials. More particularly, the present invention relates to lithography-based patterning of fluorine-containing polymeric materials. BACKGROUND OF THE FNVENTION
  • OLEDs and PLEDs organic and polymeric light-emitting diodes
  • EL electroluminescence
  • PLEDs organic and polymeric light-emitting diodes
  • Solutions of conjugated polymers can be dispensed onto the desired area by ink-jet printing or screen printing, or form films on regions where a sacrificial photoresist material defines the target.
  • fluorinated imaging material can be used in combination with fluorous solvents to pattern a wide variety of non-fluorinated organic electronic materials, including poly(9,9-dioctylfluorene) (F8) and poly(3-hexylthiophene) (P3HT) without causing device damage.
  • fluorinated imaging material can be used in combination with fluorous solvents to pattern a wide variety of non-fluorinated organic electronic materials, including poly(9,9-dioctylfluorene) (F8) and poly(3-hexylthiophene) (P3HT) without causing device damage.
  • Another alternative approach to pattern polymer light-emitting diodes (PLEDs) uses dry photolithography (DPP) via a supercritical C0 2 process.
  • cross-linkable light-emitting polymers mentioned above also provide an approach to achieve solution-processed multi-layer OLED structures. Nevertheless, this option involves complicated chemical synthesis and requires careful polymer handling to prevent undesired cross-linking of the polymer. Moreover, curing agents are unnecessary components for device operation and even generate a significant amount of chemical residue that remains a challenge to device lifetime.
  • Materials orthogonality has been utilized to form three-layer solution-processed light-emitting devices by alternate deposition of hydrophobic polymer and hydrophilic polyelectrolyte solutions.
  • the significant amount of mobile ions carried by the polyelectrolytes is known to limit the operating lifetime.
  • the polar solvents used for dissolving electrolytes usually water or alcohols that are known to be detrimental to device carrier mobility and lifetime, thus they should be avoided during device processing.
  • the present invention provides a method for obtaining a patterned structure comprising a fluorine-containing polymeric material comprising the steps of: a) coating a substrate with a layer of fluorine-containing polymeric material; b) coating the substrate from a) with a layer of photoresist material; c) selectively exposing portions of the layer of photoresist material to radiation forming a first pattern of exposed photoresist material and a second pattern of unexposed photoresist material; d) selectively removing either the first pattern of exposed photoresist material or the second pattern of unexposed photoresist material resulting in a residual pattern in the photoresist layer; and e) transferring the residual pattern of the photoresist layer from step d) to the layer of fluorine-containing polymeric material.
  • the method is performed such that a patterned structure comprising a fluorine-containing polymeric material is formed.
  • the present invention provides a method for obtaining a patterned structure comprising a fluorine-containing polymeric material comprising the steps of: a) coating a substrate with a layer of photoresist material; b) selectively exposing portions of the layer of photoresist material to radiation forming a first pattern of exposed photoresist material and a second pattern of unexposed photoresist material; c) selectively removing either the first pattern of exposed photoresist material or the second pattern of unexposed photoresist material resulting in a residual pattern in the photoresist layer; d) coating the substrate from c) with a layer of fluorine-containing polymeric material; and e) removing the residual pattern of photoresist material and fluorine-containing polymeric material corresponding to the residual pattern of photoresist material leaving a second residual pattern of fluorine-containing polymeric material on the substrate.
  • the method is performed such that a patterned structure comprising a fluorine-containing polymeric material is
  • the fluorine-containing polymeric material comprises a fluorine-containing polymer or fluorine-containing copolymer.
  • the fluorine-containing polymer or copolymer is formed at least in part from a fluorine-containing monomer comprising an active-moitety and a flurorine-containing moiety. In one example, all of the fluorine in the fluorine-containing monomer is located in the fluorine-containing moiety.
  • the fluorine- containing moiety is attached to the active moiety by an alkyl spacer moiety.
  • the fluorine-containing polymer or fluorine-containing copolymer further comprises a moiety selected from benzotriazole, benzothiadiazole, thiophene-benzothiadiazole-thiophene moiety and combinations thereof.
  • the present invention provides a patterned structure of fluorine- containing polymeric material. Such materials can be obtained by the methods disclosed herein.
  • the present invention provides a device comprising the patterned structure of fluorine-containing polymeric material, such as those obtained by the methods disclosed herein.
  • the device can comprise three patterned fluorine-containing organic structure layers, where one layer is capable of emitting red light, a second layer is capable of emitting green light and a third layer is capable of emitting blue light.
  • all three individual patterned fluorine-containing organic structure layers can have the same pattern and are stacked such that the resulting composite pattern is the same as any of the individual layer patterns.
  • Figure 1 Chemical structures of (a) HFE-7500, and (b) examples of fluorinated materials (semi-perfluoroalkyl polyfluorenes).
  • FIG. 1 Synthesis scheme for examples of monomers and polymers. Reagents and conditions: (a) NaOH, Bu 4 NBr, toluene + water, 80 °C, overnight; (b) tBuLi, 2-isopropoxy- 4,4,5,5-tetramethyl[l,3,2]dioxaborolane, THF, -78 °C ⁇ room temperature, 1.5 hours; (c) n BuLi, 2 (1 eq.), THF, -78 °C ⁇ room temperature, 1 hour, this sequence repeated once more; (d) Br 2 with cat.
  • Figure 3 (a) Example of an EL spectra of PR F F12 and the reference polymer PF12. (b) Example of statistical random copolymer, P(R F F12-R F BTz), composed of semi- perfluoroalkyl fluorene and semi-perfluoroalkyl benzotriazole units, (c) Example of current- voltage-luminance plot of PR F F12 and P(R F F12-R F BTZ). (d) Example of UV-Vis absorption and EL spectra of P(R F F12-R F BTz).
  • Figure 4. (a) Example of scheme of patterning using PR F F12 and a conventional photoresist, (b) Example of photo luminescence image of patterned PR F F12 under fluorescence microscope, (c) Example of operating EL pixels constructed using P(RF F 12-R F BTz).
  • Figure 10 Example of 1H NMR (400 MHz) spectrum of P(R F F 12-R F BTz) in a mixed solvent of CDC1 3 (1 part by vol.) and CFC1 3 (1 part by vol.). [0023] Figure 11. Example of TGA thermograms of PR F F 10, PR F F 12, PR F F 14 and PF 12
  • Figure 15 Example of calculated HOMO and LUMO energy levels (unit is eV) for a single monomer unit R F F10, R F F12, R F F14 and F12 vs. vacuum level.
  • Figure 17 (a) Examples of polymer structures of R F -B, R F -G, and R F -R polymers.
  • FIG. 1 Example of single-layer R F -LEP devices of R F -B, R F -G and R F -R (a) Example of current- voltage characteristics, (b) Example of luminance-voltage characteristics, (c)
  • Example of current efficiency (d) Example of EL spectra, and (e) Example of absorption spectra.
  • Figure 19 Example of operation of a single layer R F -G device after chloroform immersion. Example of current- voltage-luminescence characteristics and current efficiency of immersed and reference devices.
  • F8/R F -G/R F -R devices with comparison between thin (60 nm) and thick (160 nm) R F -G layers (device structure shown in inset), (b) Tri-layer F8/R F -R/R F -G devices (device structure shown in inset).
  • Figure 21 (a) Example of a schematic diagram of patterning process for RGB array via a dry etch process, (b) Example of photo luminescence image of RGB individual 3 x 3 pixel array.
  • the present invention is directed to methods of patterning of fluorine-containing materials, patterned structures of fluorine-containing materials, the devices comprising patterned structures of fluorine-containing materials.
  • the patterned structures maintain desirable properties (e.g., physical/mechanical properties and/or chemical/electrical/optical properties) on exposure to conventional process materials (e.g., solvents such as non-polar organic solvents, polar organic solvents and aqueous-based solvents used in lithographic patterning processes).
  • solvents such as non-polar organic solvents, polar organic solvents and aqueous-based solvents used in lithographic patterning processes.
  • An orthogonal combination of materials e.g., fluorinated functional polymers with conventional photoresists and solvents, can be used for device patterning.
  • Fluorinated polymer films with sufficient fluorine content remain intact and substantially unaffected when exposed to aqueous-based or organic solvents, even without cross-linking.
  • substantially unaffected it is meant that the physical and/or mechanical properties and/or chemical and/or electrical and/or optical properties, as appropriate for the specific material, are degraded by 10% or less. In various embodiments, the properties are degraded by 5% or less, 4% or less, 3% or less, 2%> or less and 1% or less.
  • Fluorinated light-emitting polymers that are processable in fluorous solvents, such as HFEs can be patterned using conventional patterning processes based on conventional photoresists and solvents.
  • a blue-emitting polymer, polyfluorene, the F content of which can be controlled by introducing suitable perfluoroalkyl moieties at the 9 position of 9H-fluorene can be patterned according to the present invention. It is expected that this approach can be applied to, for example, other fluorene-containing polymers, including light-emitting polymers and other fluorine-containing polymeric materials.
  • the present invention provides methods of patterning of fluorine- containing materials, such as fluorine-containing polymeric materials.
  • fluorine-containing materials can be patterned using conventional positive- and/or negative-tone photoresist based processes.
  • a method for obtaining a patterned structure comprising a fluorine-containing polymer material comprising the steps of: a) coating a substrate with a layer of fluorine-containing polymeric material; b) coating the substrate from a) with a layer of photoresist material; c) selectively exposing portions of the layer of photoresist material to radiation forming a first pattern of exposed photoresist material and a second pattern of unexposed photoresist material; d) selectively removing either the first pattern of exposed photoresist material or the second pattern of unexposed photoresist material resulting in a residual pattern in the photoresist layer; and e) transferring the residual pattern of the photoresist layer from step d) to the layer of fluorine-containing polymeric material.
  • This process results in formation of a patterned structure of fluorine-containing polymeric material.
  • pattern transfer e.g., transfer of the residual pattern from step d) as set out above, is carried out by dry etch (e.g., oxygen plasma etch) processing.
  • dry etch e.g., oxygen plasma etch
  • any residual photoresist or other residual material can be removed. Methods of removing such materials is well-known in the art.
  • a method for obtaining a patterned structure comprising a fluorine-containing polymeric material comprising the steps of: a) coating a substrate with a layer of photoresist material; b) selectively exposing portions of the layer of photoresist material to radiation forming a first pattern of exposed photoresist material and a second pattern of unexposed photoresist material; c) selectively removing either the first pattern of exposed photoresist material or the second pattern of unexposed photoresist material resulting in a residual pattern in the photoresist layer; d) coating the substrate from c) with a layer of fluorine- containing polymeric material; and e) removing the residual pattern of photoresist material and fluorine-containing material corresponding to the residual pattern of photoresist material leaving a second residual pattern of fluorine containing material on the substrate.
  • This process results in formation of a patterned structure of fluorine-containing polymeric material. In various examples, such a process is
  • Structures having a feature size (minimum length) of, for example, 50 nm to 500 microns can be formed using the methods disclosed herein.
  • structures formed using methods utilizing photolithographic patterning can have a dimensions resulting from the lithographic patterning process used.
  • Structures with a wide range of thicknesses can be produced using the methods and materials described herein.
  • the thickness of structures can be from 5 nm to 10 microns.
  • the substrate can have any desired size or thickness.
  • any substrate which can be used in conventional photolithography or other patterning processes can be used.
  • the substrate can be formed from any material so long as the substrate has a surface with properties (e.g., physical properties and chemical properties) such that a layer of fluorine- containing material and/or photoresist can be formed.
  • the substrate can be coated with another material or multiple layers of materials (e.g., a conducting or semi-conducting material). If the substrate is coated with such a material or materials, the outermost layer of the coated substrate must provide a surface with properties (e.g., chemical and physical properties) such that a layer of fluorine-containing material and/or photoresist can be formed.
  • suitable substrate materials include, but are not limited to, silicon, silicon dioxide, silicon nitride, silicon germanium, glass, polymeric materials (such as organic polymeric materials), and the like.
  • coated substrates include, but are not limited to, substrates coated with indium tin oxide (ITO).
  • ITO indium tin oxide
  • the processes disclosed herein can use any photoresist material which is compatable with process solvents that do not adversely affect the fluorine-containing polymer materials.
  • An example, such a photoresist is compatible with process solvents that do not detectibly effect the desirable physical/mechanical properties and/or chemical/electrical/optical properties of fluorine-containing polymeric materials.
  • Examples of such photoresist materials are well known in the art. Examples of photoresist are well-known in the art and include
  • Both positive-tone and negative-tone photoresists can be used. In some embodiments, it can be desirable that the photoresist not contain fluorine.
  • the selected portions of the photoresist are removed by contact with an appropriate solvent (e.g., solvents such as non-polar organic solvents, polar organic solvents and aqueous-based solvents).
  • solvents e.g., solvents such as non-polar organic solvents, polar organic solvents and aqueous-based solvents.
  • the fluorine-containing polymeric material is any material with sufficient fluorine content such that it can be deposited as a layer on the substrate and patterned according to the methods disclosed herein and the properties (e.g., physical/mechanical and/or
  • the fluorine-containing material has 20% or more by weight fluorine content.
  • the fluorine content can be at least 25% or more, 30% or more, 35% or more, 40% or more, 45% or more or 50% or more by weight, including all integers between 20%> by weight and 50%> by weight.
  • the fluorine-containing polymeric material comprises a fluorine-containing polymer or fluorine-containing copolymer.
  • the fluorine-containing polymer or copolymer comprises a fluorine-containing monomer (i.e., the fluorine-containing polymer or copolymer is made by a polymerization reaction the uses, at least in part, a fluorine-containing monomer).
  • the fluorine-containing polymer or copolymer is formed at least in part from a fluorine-containing monomer comprising an active -moiety and a flurorine- containing moiety, wherein all of the fluorine in the fluorine-containing monomer is located in the fluorine-containing moiety.
  • the active moiety comprises a group or groups exhibiting a property or properties such as, for example, light-emitting behavior (e.g., fluorescence or electroluminescene), electron- transport behavior (e.g., electron-transport semiconductors), are useful materials for biological applications and the like.
  • light-emitting behavior e.g., fluorescence or electroluminescene
  • electron- transport behavior e.g., electron-transport semiconductors
  • An example of an active moiety is a fluorene group that exhibits light- emitting behavior.
  • the fluorine-containing moiety comprises a group or groups that contain fluorine such that the desired fluorine content of the polymer is achieved.
  • the fluorine-containing moiety can, for example, comprise a perfluoroalkyl group.
  • the fluorine-containing moiety can be attached to the active moiety by an alkyl spacer moiety that contains, for example, from 1 carbon to 10 carbons, including all integers between 1 carbon and 10 carbons.
  • the fluorine-containing polymer or copolymer can also contain benzotriazole moieties, benzothiadiazole moieties, thiophene-benzothiadiazole-thiophene moieties and combinations thereof. These moieties can, optionally, be fluorinated, for example, in a similar manner as disclosed herein.
  • the fluorine-containing polymer or fluorine-containing copolymer comprises a moiety selected from the following structures:
  • R 1 and R 2 are each independently a fluorine-containing moiety (e.g., a perfluoroalkyl moiety) having from 1 carbon to 12 carbons, including all values between 1 carbon and 12 carbons.
  • the values of n and m are each independently from 1 to 10, including all integers between 1 and 10.
  • the value of k is from 2 to 1,000, including all integers between 2 and 1,000.
  • the fluorine-containing material is a copolymer having the following structure:
  • E is a group comprising moieties such as, for example, benzotriazole moieties, benzothiadiazole moieties, thiophene-benzothiadiazole-thiophene moieties and combinations thereof.
  • the E group can, optionally, be fluorinated, for example, in a similar manner as disclosed herein.
  • the fluorine-containing copolymer can have the following structure:
  • n, m and p are each
  • the values of s and t are independently from 1 to 20, including all values between 1 and 20.
  • the value of k is from 2 to 1,000.
  • the fluorine-containing polymers and fluorine-containing polymers copolymers of the present invention have terminal groups (also referred to as, end groups). Terminal groups and methods of introducing such groups are well-known in the art.
  • the fluorine- containing polymers and fluorine-containing polymers copolymers have end groups such as hydrogen, alkyl groups, phenyl groups, and the like.
  • the present invention provides a patterned structure of fluorine-containing polymer material.
  • a patterned structure of fluorine-containing polymer material can be a patterned fluorine-containing organic structure comprising a fluorine- containing polymer or copolymer described herein.
  • the steps of the method are repeated such that multiple layers of patterned structures comprising fluorine-containing polymer materials are obtained. It is desirable that the layers of patterned structures are formed with layer- to-layer registration alignment sufficient to achieve the desired device performance and/or properties. Each of the individual layers of patterned structures can comprise the same or different fluorine-containing polymer materials. An example of such a multi-layer structure is described in Example 2.
  • the present invention provides devices comprising patterned structures of fluorine-containing materials.
  • devices include, but are not limited to, devices with displays (for example, organic (e.g., polymer) light emitting diode based displays, particularly full color displays), devices for solid-state lighting applications, sensors and the like.
  • the present invention provides a device comprising a patterned fluorine-containing organic structure layer produced by the methods disclosed herein.
  • the device comprises three patterned fluorine-containing organic structure layers, wherein a first layer is capable of emitting red light, wherein a second layer is capable of emitting green light, and a third layer is capable of emitting blue light.
  • all three individual patterned fluorine-containing organic structure layers have the same pattern and are stacked such that the resulting composite pattern is the same as any of the individual layer patterns.
  • the present invention provides fluorine-containing polymers and fluorine-containing polymers copolymers.
  • the fluorine-containing polymer has the following structure:
  • the fluorine-containing copolymers have the following properties:
  • E is a group such as, for example, benzotriazole moieties, benzothiadiazole moieties, thiophene-benzothiadiazole-thiophene moieties and combinations thereof.
  • the E group can, optionally, be fluorinated.
  • the fluorine-containing copolymers have the following structure:
  • n, m and p are each independently from 1 to 10, including all values between 1 and 10.
  • s and t are independently from 1 to 20, including all values between 1 and 20.
  • k is from 2 to 1,000.
  • Perfluoroalkyl moieties are strongly electron-withdrawing, which can perturb the electronic characteristics of polyfluorenes. It is, therefore, desirable to insert suitable alkyl spacers between the polymer backbone and perfluoroalkyl moieties. In the case of monomer synthesis, the alkyl spacers give the added benefit of enabling base-assisted S N 2 reactions between semi-perfluoroalkyl halides [X-(CH 2 ) y (CF 2 ) z F] and 9H-fluorene.
  • the Suzuki cross-coupling reaction is a polymerization protocol for high molecular-weight polyfluorenes. It was chosen for synthesis of the target polymers, making it necessary to prepare semi-perfluroalkyl fluorene dibromides 5, 6 and 9 and diboronates 7, 8 and 12 ( Figure 2). Syntheses of dibromides 5 and 6 were performed conveniently through alkylation reactions of 2,7-dibromofluorene 1 with semifluorinated iodides 3 and 4 respectively under phase-transfer catalysis conditions. Each monomer was recovered in high yield after
  • the next step required the preparation of diboronates.
  • the fluorene dibromides 5 and 6 were transformed into the diboronates 7 and 8 in good yield through a series of lithiation reactions using 'BuLi and substitution with isopropoxydioxaborolane.
  • the same set of reactions did not prove effective in converting the dibromide 9 into the diboronate 12.
  • Only a large amount of the starting material 9 was recovered at the end of crystallization from acetone.
  • An alternative method employing bis(pinacolato)diboron and Pd catalyst was then applied. The reaction in DMF at 80 °C proved successful, giving the fluorene diboronate 12 in 46% yield after purification.
  • DSC Differential scanning calorimetry
  • ITO/PEDOT:PSS/light-emitting polymer/CsF/Al Films of the fluorinated polymers were deposited from solution in HFE-7500 on a hole injection layer of poly(3,4- ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS).
  • PEDOT:PSS poly(3,4- ethylenedioxythiophene):poly(styrenesulfonate)
  • PR F F I O the emission brightness from the device was below 50 cd m "2 .
  • PR F F12 and PRpF14 the devices exhibited similar emission spectra to their PL characteristics ( Figure 3a). However, the devices operated at higher voltages (> 10 V) than that of PF12 and their lifetime was short.
  • FIG. 4a A simplified process scheme is depicted in Figure 4a.
  • a commercial photoresist was first patterned lithographically on a Si wafer to make a template, onto which a solution of PRFF12 in HFE-7500 was spin-coated.
  • the patterned photoresist film was treated with trichloro(lH,lH,2H,2H-perfluorooctyl)silane vapor prior to the deposition of PR F F12.
  • Lift-off of the photoresist film in acetone produced a well-defined image of PRpF12 down to 5 ⁇ resolution ( Figure 4b). It should be noted that exposure to HFE-7500 and acetone had no adverse effect on the non- fluorinated photoresist image and the deposited PRpF12 film, respectively.
  • P(RFF12-RFBTz) The fabrication process was essentially the same as Figure 4a except that a PEDOT:PSS film was spin-coated before the deposition of a P(RFF12-RFBTz) layer and a
  • Inova-500 500 MHz
  • spectrometer at ambient temperature, using the chemical shift of a residual protic solvent (CHCI 3 at ⁇ 7.28 ppm) as an internal reference. All chemical shifts are quoted in parts per million (ppm) relative to the internal reference and coupling constants J are measured in Hz.
  • the multiplicity of the signal is indicated as follows: s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet), dd (doublet of doublets), dt (doublet of triplets), dm (doublet of multiplets), br s (broad singlet) and br d (broad doublet).
  • the thermal transition behavior of polymers was measured on a TA Instruments Q1000 modulated differential scanning calorimeter (DSC) at a heat/cool rate of 10 °C min "1 under N 2 for three heat/cool cycles. Size exclusion chromatography was performed on a Waters GPC system (Waters 486 UV detector) by eluting THF (1 cm 3 min "1 ) at 40 °C, or by Asahi Glass Co. Ltd. (Japan) using dichloropentafluoropropanes as an eluant according to a published procedure. UV- Vis absorption spectra were recorded on a Shimadzu UV-3101PC (source change at 320 nm and interval 1 nm). Photo luminescence and electroluminescence spectra were recorded on an
  • Non-perfiuoroalkyl fluorene monomers and the corresponding polymer (PF12) as a reference material 2,7-Dibromo-9,9-didodecylfiuorene 13.
  • 2,7-dibromofiuorene 1 3.00 g, 9.26 mmol
  • 1-iodododecane 6.86 g, 23.1 mmol
  • toluene (10 cm 3 ) 50% (w/w) NaOH aqueous solution (20 g) and Bu 4 NBr (0.30 g, 0.93 mmol). The mixture was then heated to 80 °C.
  • the spin-coating solvent was benzotrifluoride; PF12 was spin coated on a Si wafer which had been treated with 1,1, 1,3,3, 3-hexamethyldisilazane in advance.
  • the spin-coating solvent was / ⁇ -xylene.
  • UV-Vis, PL and EL properties characterization UV-Vis, PL and EL properties characterization. UV-Vis and PL spectra (see
  • PEDOT:PSS was spin-coated at 5000 rpm and subsequently baked at 180 °C for 40 min under a N 2 atmosphere.
  • the fluorescent polymers were then spin-coated from their HFE-7500 solutions (in cases of semi-perfluoroalkyl polyfluorenes) or / ⁇ -xylene solutions (in the case of non- fluorinated polymer) under a N 2 atmosphere and further baked at 100 °C for 1 hour prior to the deposition of a top cathode of CsF (1 nm)/Al (40 nm).
  • the deposition rate of CsF was 0.1 nm s "1 .
  • the sample active area was 0.03 cm 2 .
  • PRpF12 solution in HFE- 7500 was spin-coated to give ca. 50 nm thick film.
  • the wafer was then emerged into acetone for 1 minute to remove the photoresist film.
  • Resulting PR F F12 image was examined under a fluorescence microscope. (See, e.g., Figure 16)
  • RF-LEP highly fluorinated light-emitting polymer
  • BTMB bis(trifluoromethyl)benzene
  • HFEs hydrofluoroethers
  • TMAH tetramethyl ammonium hydroxide
  • PMEA propylene glycol methyl ether acetate
  • RF-G and R Two new RF- LEPs for green (RF-G) and red (RF-R) emission are also synthesized by replacing the BTz comonomer with benzothiadiazole (BT) and thiophene-benzothiadiazole-thiophene (TBT), respectively.
  • Fig. 17(a) shows the chemical structures of highly fluorinated polymers RF-B, RF- G, and RF-R. Details of the synthesis of these polymers can be found in the supporting information. The fluorine content of these polymers is ca. 58% (RF-B), 56% (RF-G), and 55% (RF-R). All these polymers consist of semi-perfluoroalkyl side chains of to facilitate dissolution in fluorinated solvents.
  • the highest occupied molecular orbital (HOMO) of the RF-LEPs is around 5.8 eV, observed by photoelectron spectroscopy in air (PES A).
  • the lowest unoccupied molecular orbital (LUMO) varies from 3.2 to 3.9eV (estimated by adding the optical band gap to the HOMO value), as shown in Fig. 17(b). Electron injection into these RF- LEPs from various low work function metal cathodes is thus energetically favourable.
  • Figs. 18(a)-(b) show the current- voltage-luminescence (IVL) characteristics of the single layer devices. Devices have turn-on voltages (defined by luminance of 1 cd/m 2 ) of 4 V, 6 V, and 4.5 V for RF-R, RF-G and RF-B, respectively. The corresponding current efficiencies are 0.75 cd/A, 6.8 cd/A, and 0.15 cd/A at the current density of 1 mA/cm 2 , with peak
  • EL electroluminescence
  • RF-R 632 nm
  • RF-G 535 nm
  • RF-B 482 nm
  • the single layer RF-G device performance compares favorably to the 5-10 cd/A efficiency achieved by high performance PLEDs based on poly(9,9- dioctylfluorene-alt-benzothiadiazole) (F8BT), which is the analogous non-fluorinated polymer.
  • F8BT poly(9,9- dioctylfluorene-alt-benzothiadiazole)
  • Their corresponding absorption spectra are shown in Figure 18(e), illustrating their respective optical band gaps of 1.9, 2.4, 2.6 eV, extracted through the Tauc plot given in the inset.
  • RF-LEPs can be stacked by spin-coating to form bi-layers.
  • BTMB bis(trifluoromethyl)benzene
  • BTF benzotrifluoride
  • Figure 20(a) illustrates the device characteristics of a tri-layer red-emitting device with a thin RF-R layer on top of a thin RF-G layer (60 nm), and PEDOT:PSS/F8 (40 nm) as the underlying layers.
  • FIG. 21(b) shows a photo luminescence (PL) image of the patterned RGB array under ultraviolet light (365 nm). Each pixel is 140 ⁇ by 140 ⁇ in size. These patterned RGB pixels demonstrate the viability of patterning RF-LEP using an ordinary photolithographic approach employing organic solvents and aqueous photoresist processing conditions.
  • the fluorinated functional materials have been shown to be robust and exhibit high chemical stability. These unique properties provide great flexibility in device structure design and processing. These methods and materials are of interest to, for example, to the large- area, flexible electronics community.
  • RGB PLED fabrication procedure Devices have a structure of ITO / PEDOT:PSS
  • Fluorinated light emitting polymers can be dissolved in a variety of fluorinated solvents, including
  • HFEs hydrofluoroethers
  • BTMB bis(trif uoromethyl)benzene
  • BTF benzotrifluoride
  • RF-LEP was dissolved at a concentration of 10-20 mg/mL in the solvents mentioned above by stirring at room temperature.
  • the polymer solutions were then spin-coated without further filtration to form films with thickness ranging from 100-200 nm, which were baked at 100 °C for 15 minutes in N 2 .
  • Top Ca/Al cathode was thermally evaporated at a base pressure of 10-6 Torr at a rate of 0.2 nm/s and 0.1 nm/s, respectively.
  • Tri-layer red-emitting device has a structure of ITO / PEDOT:PSS (AI4083) / F8 /
  • ITO glass substrates and PEDOT:PSS layers were prepared as above.
  • the first buffer layer of 40 nm thick poly(9,9- dioctylfluorene) (F8) was formed by spin-coating at 2000 rpm from a 10 mg/ml solution in p- xylene, and then baked at 130 °C for 15 min in N 2 .
  • the first LEP layer was spin-coated at 700 rpm from a RF-G solution of either 5 or 20 mg/mL in BTF to form a thin (60 nm) or a thick (160 nm) RF-G film respectively.
  • This RF-G layer is further baked at 150 °C for 30 min in N 2 .
  • a second layer of RF-R was then spin-coated at 700 rpm from a RF-R solution of 7.5 mg/mL in BTMB.
  • the RF-R layer was spin-coated at 1500 rpm from a 7.5 mg/mL solution in BTMB to form a 20 nm film, and baked at 150 °C for 30 min in N 2 .
  • the second layer of RF-G is then spin-coated at 700 rpm from a 10 mg/mL solution in BTMB and further baked at 150 °C for 15 min in N 2 .
  • Pattern transfer from the photoresist image to the RF-G was achieved by dry etching in oxygen plasma using an Oxford PlasmaLab 80+ RIE System. RF-R solution was then spin-coated on top of the patterned RF-G pixels, and the same procedure was repeated. Finally, RF-B solution was spin-coated on top of the patterned RF-G and RF-R pixels and then patterned as above, to produce the green, red and blue pixels. Remaining photoresist was removed with Shipley Microposit 1165 resist remover and acetone.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Structural Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Architecture (AREA)
  • Materials Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne des procédés et des compositions pour obtenir des structures à motifs comprenant des matériaux polymères contenant du fluor. Les matériaux polymères contenant du fluor ont une teneur en fluor suffisante pour que des motifs puissent être dessinés sur les matériaux en utilisant des procédés de transfert de motifs/photolithographiques conventionnels et gardent des propriétés physiques et mécaniques souhaitables. Les structures à motifs peuvent être utilisées, par exemple, dans des dispositifs émettant de la lumière.
EP10825580.3A 2009-10-20 2010-10-20 Procédés de fabrication de structures à motifs à partir de matériaux polymères contenant du fluor et polymères contenant du fluor Withdrawn EP2491458A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US25338109P 2009-10-20 2009-10-20
PCT/US2010/053356 WO2011050048A2 (fr) 2009-10-20 2010-10-20 Procédés de fabrication de structures à motifs à partir de matériaux polymères contenant du fluor et polymères contenant du fluor

Publications (2)

Publication Number Publication Date
EP2491458A2 true EP2491458A2 (fr) 2012-08-29
EP2491458A4 EP2491458A4 (fr) 2013-06-12

Family

ID=43900927

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10825580.3A Withdrawn EP2491458A4 (fr) 2009-10-20 2010-10-20 Procédés de fabrication de structures à motifs à partir de matériaux polymères contenant du fluor et polymères contenant du fluor

Country Status (5)

Country Link
US (1) US8809111B2 (fr)
EP (1) EP2491458A4 (fr)
KR (1) KR101771978B1 (fr)
CN (1) CN102667626B (fr)
WO (1) WO2011050048A2 (fr)

Families Citing this family (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9259759B2 (en) 2010-03-01 2016-02-16 Cornell University Patterning of biomaterials using fluorinated materials and fluorinated solvents
GB2483269A (en) * 2010-09-02 2012-03-07 Cambridge Display Tech Ltd Organic Electroluminescent Device containing Fluorinated Compounds
CN103159924A (zh) * 2011-12-09 2013-06-19 海洋王照明科技股份有限公司 苯并三唑基共聚物太阳能电池材料及其制备方法和应用
CN103159916A (zh) * 2011-12-09 2013-06-19 海洋王照明科技股份有限公司 二氟代苯并三唑基共聚物有机半导体材料及其制备方法和应用
US9298088B2 (en) * 2013-07-24 2016-03-29 Orthogonal, Inc. Fluorinated photopolymer with fluorinated sensitizer
US9958778B2 (en) 2014-02-07 2018-05-01 Orthogonal, Inc. Cross-linkable fluorinated photopolymer
DE102014117096B4 (de) * 2014-04-01 2018-06-21 Technische Universität Dresden Fotolithografieverfahren zum Herstellen organischer Leuchtdioden
EP3175495B1 (fr) 2014-08-01 2020-01-01 Orthogonal Inc. Modelage photolithographique de dispositifs
CN107112418B (zh) 2014-08-01 2021-01-15 正交公司 有机电子装置的光刻法图案化
US9899636B2 (en) 2014-08-01 2018-02-20 Orthogonal, Inc. Photolithographic patterning of organic electronic devices
JP2017526177A (ja) * 2014-08-01 2017-09-07 オーソゴナル，インコーポレイテッド 素子のフォトリソグラフパターン化方法
KR102552276B1 (ko) 2015-02-24 2023-07-07 삼성디스플레이 주식회사 유기 발광 표시 장치 및 그 제조 방법
KR102421582B1 (ko) 2015-02-24 2022-07-18 삼성디스플레이 주식회사 유기 발광 표시 장치 및 그 제조 방법
KR102614598B1 (ko) 2016-06-27 2023-12-18 삼성디스플레이 주식회사 유기 발광 표시 장치
WO2020163762A1 (fr) * 2019-02-07 2020-08-13 Orthogonal, Inc. Structures de réserve en fluoropolymère ayant un profil en contre-dépouille
CN110981829A (zh) * 2019-12-16 2020-04-10 南昌航空大学 高空气稳定性阴极界面层的制备方法
KR102412986B1 (ko) * 2021-07-05 2022-06-27 덕산네오룩스 주식회사 유기전기 소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치
US11856841B2 (en) 2021-07-05 2023-12-26 Duk San Neolux Co., Ltd. Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1261044A2 (fr) * 2000-09-25 2002-11-27 Dai Nippon Printing Co., Ltd. Procédé de fabrication d'un dispositif organique électroluminescent
US20040062930A1 (en) * 2002-09-25 2004-04-01 3M Innovative Properties Company Electroactive polymers
WO2007057664A2 (fr) * 2005-11-17 2007-05-24 Imperial College Innovations Limited Procede de dessin d'un film mince
WO2011004198A2 (fr) * 2009-07-10 2011-01-13 Cambridge Enterprise Limited Formation de motifs

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4978594A (en) * 1988-10-17 1990-12-18 International Business Machines Corporation Fluorine-containing base layer for multi-layer resist processes
JP3074634B2 (ja) * 1994-03-28 2000-08-07 三菱瓦斯化学株式会社 フォトレジスト用剥離液及び配線パターンの形成方法
JP2003034705A (ja) 2001-07-24 2003-02-07 Nec Corp フッ素含有フェニルマレイミド誘導体、重合体、化学増幅レジスト組成物及びそれを用いたパターン形成方法
JP3666807B2 (ja) 2001-12-03 2005-06-29 東京応化工業株式会社 ホトレジストパターンの形成方法およびホトレジスト積層体
JP2008060552A (ja) * 2006-08-02 2008-03-13 Osaka Univ 電子回路装置とその製造方法
JP5723626B2 (ja) 2010-02-19 2015-05-27 富士フイルム株式会社 パターン形成方法、化学増幅型レジスト組成物及びレジスト膜
US9264198B2 (en) * 2011-02-28 2016-02-16 Qualcomm Incorporated Methods and apparatus for employing different capabilities for different duplexing modes

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1261044A2 (fr) * 2000-09-25 2002-11-27 Dai Nippon Printing Co., Ltd. Procédé de fabrication d'un dispositif organique électroluminescent
US20040062930A1 (en) * 2002-09-25 2004-04-01 3M Innovative Properties Company Electroactive polymers
WO2007057664A2 (fr) * 2005-11-17 2007-05-24 Imperial College Innovations Limited Procede de dessin d'un film mince
WO2011004198A2 (fr) * 2009-07-10 2011-01-13 Cambridge Enterprise Limited Formation de motifs

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2011050048A2 *

Also Published As

Publication number Publication date
CN102667626A (zh) 2012-09-12
US20120305897A1 (en) 2012-12-06
EP2491458A4 (fr) 2013-06-12
WO2011050048A3 (fr) 2011-10-06
KR20120095927A (ko) 2012-08-29
US8809111B2 (en) 2014-08-19
CN102667626B (zh) 2014-11-19
KR101771978B1 (ko) 2017-08-28
WO2011050048A2 (fr) 2011-04-28

Similar Documents

Publication Publication Date Title
US8809111B2 (en) Methods of making patterned structures of fluorine-containing polymeric materials and fluorine-containing polymers
US8530269B2 (en) Manufacture of a polymer device
US9500952B2 (en) Orthogonal processing of organic materials used in electronic and electrical devices
Fong et al. Orthogonal processing and patterning enabled by highly fluorinated light-emitting polymers
KR101366354B1 (ko) 방사선 가교제
EP2960280A1 (fr) Compositions photo-réticulables, des couches minces diélectriques structurées ayant un valeur k élevé et des appareils contentants celles-ci.
JP5744061B2 (ja) 有機ｅｌ素子およびその製造方法
CN104011895A (zh) 制造内含层的方法和材料以及由其制成的器件
Lee et al. Semiperfluoroalkyl polyfluorenes for orthogonal processing in fluorous solvents
EP2507309A1 (fr) Fraction de réticulation
Solomeshch et al. Electronic formulations—Photopatterning of luminescent conjugated polymers
JP7310349B2 (ja) 有機ｅｌ表示装置
CN1809935B (zh) 聚合物器件的制备
KR102547153B1 (ko) 유기 발광 복합체 및 이를 포함하는 유기 발광 박막의 패터닝 방법, 이를 포함하는 유기 발광 조성물, 이를 포함하는 유기 발광 소자
TW202039250A (zh) 積層體、有機半導體元件及它們的製造方法、以及組成物及所述組成物的套組
WO2012085985A1 (fr) Composé polymère et son procédé de production
JP2022134244A (ja) 電子デバイスの製造方法
Scheler et al. Synthesis and Properties of Alternating Fluorene‐Based Oligomers for Sub‐µm Photopatterning
CN104838513A (zh) 用于制备内含层的方法和材料以及由其制成的设备

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120518

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20130510

RIC1 Information provided on ipc code assigned before grant

Ipc: G03F 7/11 20060101ALI20130503BHEP

Ipc: G03F 7/20 20060101AFI20130503BHEP

Ipc: G03F 7/004 20060101ALI20130503BHEP

Ipc: H01L 51/00 20060101ALI20130503BHEP

Ipc: H01L 21/027 20060101ALI20130503BHEP

17Q First examination report despatched

Effective date: 20140703

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: CORNELL UNIVERSITY

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20201125